JP6864867B2 - Containment body - Google Patents

Description

The present invention relates to ink compositions and inclusions.

The inkjet recording method is a relatively simple device that can record high-definition images, and is rapidly developing in various fields. Among them, various studies have been made on obtaining more stable and high-quality recorded materials.

For example, Patent Document 1 describes an ink container that can be attached to and detached from a liquid supply device that supplies a liquid to a liquid injection device for the purpose of setting a preferable size for the liquid container, and is flexible. An ink bag in which at least two films are bonded to each other in a state of facing each other and ink can be stored between the at least two films, and a handle portion located at the end of the ink bag and protruding outward of the ink bag. The handle portion is formed with an opening that penetrates in the first direction, which is the direction in which the at least two films face each other, and the opening size of the opening in a specific direction is 80 mm to 120 mm. A liquid container is disclosed, which is within a range and in which the width dimension of the ink bag in a particular direction is within the range of 50 mm to 300 mm.

Japanese Unexamined Patent Publication No. 2016-22637

The ink composition having a pigment as a coloring material can contain resin particles in order to improve the fastness of printed matter. In this case, since the resin particles act as a binder, the pigment can be reliably fixed on the recording medium, so that the printed matter has excellent fastness.

Here, when a conventional ink composition containing resin particles is stored and used in a storage portion made of a flexible film provided in a liquid container as described in Patent Document 1, the ink composition is used. Due to the uneven distribution of the films downward due to gravity, the films are stuck to each other via a small amount of the ink composition at the upper accommodating portion of the liquid accommodating body. In the ink composition existing at the place where the films are stuck to each other, the moisture is absorbed by the film, the balance (ratio) of the hydrophilic component and the hydrophobic component of the ink composition changes, and the distance between the resin particles is short. As a result, the resin particles are likely to aggregate, and foreign matter derived from the resin particles may be generated in the liquid container. Since the content of the resin particles in the ink composition is reduced due to the generation of foreign substances, it becomes difficult to obtain excellent fastness of the printed matter. In addition, when the ink composition is ejected by the inkjet method, foreign matter is also ejected, so that continuous printing is inferior in stability.

Therefore, the present invention has been made to solve the above-mentioned problems, and even when the printed matter is stored in a housing portion made of a flexible film and used, the printed matter has excellent fastness. It is an object of the present invention to provide an ink composition capable of obtaining the above.

As a result of diligent studies to solve the above problems, the present inventors have made an ink composition containing resin particles, a pigment, glycol ether, and water, and the volume average particle diameter of D50 of the resin particles satisfies a predetermined relational expression. However, the present invention has been completed by finding that a printed matter having excellent printed matter fastness can be obtained even when the printed matter is accommodated in an accommodating portion made of a flexible film.

That is, the present invention is an ink composition containing resin particles, a pigment, glycol ether, and water, and the resin particles satisfy the condition represented by the following relational expression (1).
1.0 ≤ (φ2 / φ1) ≤ 12.5 ... (1)
(In the formula, φ1 indicates the volume average particle diameter of D50 of the resin particles in a solution containing 20% by mass of the resin particles and 80% by mass of water, and φ2 is 90% by mass of the resin particles and 10 The volume average particle diameter of D50 of the resin particles in the solution containing mass% of water is shown.)

The factors by which the ink composition according to the present invention can solve the problem of the present invention are considered as follows. However, the factors are not limited to this. That is, the ink composition according to the present invention mainly satisfies the condition that the volume average particle diameter of D50 of the resin particles satisfies the condition represented by the above relational expression (1). Even when the films are stuck together via a small amount of ink composition, the resin particles are present even in the ink composition existing at the place where the films are stuck together, that is, in the ink composition having a reduced water content. It suppresses the deterioration of dispersibility and the aggregation of resin particles. As a result, the generation of foreign substances derived from the resin particles is suppressed, and the resin particles in the ink composition can maintain a desired content, so that a printed matter having excellent printed matter fastness can be obtained. In addition, in this specification, a "particle size" means a volume average particle size.

Further, in the ink composition according to the present invention, it is preferable that the resin particles satisfy the condition represented by the following relational expression (2).
1.0 ≤ (φ4 / φ3) ≤ 20 ... (2)
(In the formula, φ3 indicates the volume average particle diameter of D50 of the resin particles in a solution containing 20% by mass of the resin particles, 5% by mass of triethylene glycol monobutyl ether and 75% by mass of water, and φ4 is The volume average particle diameter of D50 of the resin particles in a solution containing 90% by mass of the resin particles, 5% by mass of triethylene glycol monobutyl ether and 5% by mass of water is shown.)

Further, in the ink composition according to the present invention, it is preferable that the pigment is a self-dispersing pigment satisfying the condition represented by the following relational expression (3).
1.0 ≤ (φ6 / φ5) ≤ 10 ... (3)
(In the formula, φ5 represents the volume average particle diameter of D50 of the self-dispersing pigment in a solution containing 20% by mass of the self-dispersing pigment and 80% by mass of water, and φ6 is 90% by mass of the said self-dispersing pigment. The volume average particle diameter of D50 of the self-dispersing pigment in a solution containing the self-dispersing pigment and 10% by mass of water is shown.)

Furthermore, in the ink composition according to the present invention, the glass transition temperature of the resin particles is preferably −50 ° C. or higher and 0 ° C. or lower, and the resin particles are (meth) acrylic resin, urethane resin, epoxy resin, or the like. It is preferable to contain one or more selected from the group consisting of polyolefin resin and styrene-acrylic resin, and the content of the resin particles is 0.5% by mass or more with respect to the total amount of the ink composition. The amount is preferably 5.0% by mass or less, and the pigment is preferably a carbon black pigment that has been subjected to ozone oxidation treatment, and the zeta of the resin particles in a solution containing 20% by mass of the resin particles and 80% by mass of water. The potential is preferably −60 mV or more and -15 mV or less.

In addition, the present invention comprises an accommodating portion made of a flexible film and an ink composition according to the present invention accommodated in the accommodating portion, and the water absorption rate of the film is 3% or less. Is a containment body. Further, in the container according to the present invention, it is preferable that the film has two or more layers, and the two or more layers include a layer containing at least nylon.

It is a perspective view which shows the main structure of the printing apparatus in this embodiment. It is a perspective view which shows the ink containing body in this embodiment. It is a perspective view which shows the ink containing body in this embodiment. It is a perspective view which shows the ink containing body in this embodiment. It is a perspective view which shows the ink containing body in this embodiment. It is an exploded perspective view which shows the ink containing body in this embodiment.

Hereinafter, embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary, but the present invention is not limited thereto, and a gist thereof. Various deformations are possible within the range that does not deviate from.

[Ink composition]
The ink composition of the present embodiment (hereinafter, also simply referred to as “ink composition”) contains resin particles, a pigment, glycol ether, and water. Further, the resin particles contained in the ink composition of the present embodiment satisfy the conditions represented by the following relational expression (1).
1.0 ≤ (φ2 / φ1) ≤ 12.5 ... (1)
(In the formula, φ1 indicates the volume average particle diameter of D50 of the resin particles in the solution containing 20% by mass of the resin particles and 80% by mass of water, and φ2 is 90% by mass of the resin particles and 10% by mass. The volume average particle diameter of D50 of the resin particles in the solution containing water is shown.)

Even when such an ink composition is housed in an accommodating portion made of a flexible film and used, the factors that can obtain a printed matter having excellent printed matter fastness are considered as follows. ing. However, the factors are not limited to this. That is, in the ink composition of the present embodiment, mainly when the volume average particle diameter of D50 of the resin particles satisfies the condition represented by the above relational expression (1), the ink composition on the upper side of the liquid container can be used. Even if the films are stuck together via a small amount of ink composition, the resin particles are dispersed in the ink composition existing at the place where the films are stuck together, that is, the ink composition having a reduced water content. Suppresses deterioration of sex. As a result, the generation of foreign matter is suppressed, and a printed matter having excellent printed matter fastness can be obtained. Further, since the generation of foreign substances is suppressed, the continuous printing stability is excellent when the ink composition is ejected by the inkjet method.

<Resin particles>
The resin particles of the present embodiment (hereinafter, also referred to as "resin dispersion" and "resin emulsion") are particles containing a resin. Further, the resin particles of the present embodiment satisfy the conditions represented by the following relational expression (1).
1.0 ≤ (φ2 / φ1) ≤ 12.5 ... (1)
(In the formula, φ1 indicates the volume average particle diameter of D50 of the resin particles in the solution containing 20% by mass of the resin particles and 80% by mass of water, and φ2 is 90% by mass of the resin particles and 10% by mass. The volume average particle diameter of D50 of the resin particles in the solution containing water is shown.)

Further, (φ2 / φ1) is preferably 1.0 or more and 11 or less, more preferably 1.0 or more and 10 or less, and further preferably 5.0 or more and 10 or less.

The resin particles of the present embodiment preferably satisfy the conditions represented by the following relational expression (2). As a result, the printed matter fastness and continuous print stability tend to be superior.
1.0 ≤ (φ4 / φ3) ≤ 20 ... (2)
(In the formula, φ3 indicates the volume average particle diameter of D50 of the resin particles in a solution containing 20% by mass of resin particles, 5% by mass of triethylene glycol monobutyl ether and 75% by mass of water, and φ4 is 90. The volume average particle diameter of D50 of the resin particles in the solution containing mass% resin particles, 5 mass% triethylene glycol monobutyl ether and 5 mass% water is shown.)

Further, (φ4 / φ3) is more preferably 1.0 or more and 18 or less, further preferably 1.0 or more and 16 or less, and particularly preferably 10 or more and 16 or less.

The volume average particle diameter of D50 of the resin particles in the present specification can be measured by the method described in Examples described later.

The resin particles of the present embodiment may be self-dispersion type resin particles (self-dispersion type resin particles) into which a hydrophilic component necessary for stable dispersion in water is introduced, or water by using an external emulsifier. It may be a dispersible resin particle. However, it is preferable that the resin particles are self-emulsifying resin dispersions from the viewpoint of not inhibiting the reaction with the polyvalent metal compound that can be contained in the recording medium described later.

Examples of the resin include (meth) acrylic resin, urethane resin, epoxy resin, polyolefin resin, styrene acrylic resin, fluorene resin, rosin modified resin, terpene resin, polyester resin, polyamide resin, and the like. Examples thereof include vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate-based resins. Among these, one or more selected from the group consisting of (meth) acrylic resin, urethane resin, epoxy resin, polyolefin resin, and styrene acrylic resin is preferable, and urethane resin is preferable. It is more preferable that one or more selected from the group consisting of the styrene acrylic resin and the styrene acrylic resin. These resins may be used alone or in combination of two or more.

The (meth) acrylic resin means a resin having a (meth) acrylic skeleton. The (meth) acrylic resin is not particularly limited, and is, for example, a polymer of a (meth) acrylic monomer such as (meth) acrylic acid or (meth) acrylic acid ester, or a (meth) acrylic simple resin. Examples thereof include a copolymer of a dimer and another monomer. Examples of other monomers include vinyl-based monomers such as styrene. In addition, in this specification, "(meth) acrylic" is a concept including both "methacryl" and "acrylic".

Examples of the urethane resin include a polyether type urethane resin having an ether bond in the main chain, a polyester type urethane resin having an ester bond in the main chain, and a polycarbonate type urethane resin having a carbonate bond in the main chain, in addition to the urethane bond. .. Among these, a polyester type urethane resin containing an ester bond in the main chain is preferable. These urethane resins may be used alone or in combination of two or more.

Commercially available urethane-based resins include UW-1501F, UW-5002 (above, product name manufactured by Ube Kosan Co., Ltd.), W-6061, W-6110 (above, product name manufactured by Mitsui Chemicals, Inc.) UX-150, UX-390 and UX-200 (all, trade names manufactured by Sanyo Kasei Kogyo Co., Ltd.) can be mentioned.

Examples of the styrene acrylic resin include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, 4-t-butylstyrene, chlorostyrene, vinylanisole, and vinylnaphthalene, and the above-mentioned (meth). Examples thereof include a copolymer with a monomer used for an acrylic resin, and known ones can be appropriately used. Among these, the styrene acrylic resin described in Examples described later is preferable.

The zeta (ζ) potential of the resin particles in the solution containing 20% by mass of the resin particles and 80% by mass of water is preferably −60 mV or more and -15 mV or less, more preferably −57 mV or more and -17 mV or less. More preferably, it is −55 mV or more and −20 mV or less. When the zeta (ζ) potential of the resin particles is within the above range, the generation of foreign matter is suppressed due to the fact that the resin particles are more likely to repel each other electrically, and the printed matter robustness and continuous printing stability are improved. There is a tendency.

The zeta (ζ) potential in the present specification can be measured using, for example, the “Zeta Sizar 3000HS” manufactured by Malvern (UK).

The glass transition temperature (Tg) of the resin particles is preferably −50 ° C. or higher and 0 ° C. or lower, more preferably −35 ° C. or higher and −5.0 ° C. or lower, and further preferably −20 ° C. or higher and −5 ° C. or lower. It is particularly preferably −20 or more and −10 ° C. When the glass transition temperature (Tg) of the resin particles is within the above range, the printed matter fastness and continuous print stability tend to be superior. As a method for measuring the glass transition temperature, a known measuring method can be used. For example, it is measured according to JIS K7121 (method for measuring transition temperature of plastic) using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High-Tech Science Corporation.

In the ink composition, the content of the resin particles (in terms of solid content) is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0, with respect to the total amount (100% by mass) of the ink composition. It is 5.5% by mass or more and 5.0% by mass or less, and more preferably 1.0% by mass or more and 4.0% by mass or less. When the content of the resin particles is within the above range, the printed matter fastness and continuous printing stability tend to be superior.

<Pigment>
The pigment of the present embodiment is not particularly limited, but is preferably a self-dispersing pigment. The self-dispersing pigment is a pigment having a hydrophilic group on its surface. Hydrophilic groups include -OM, -COOM, -CO- _{, -SO 3} M, -SO ₂ M, -SO ₂ NH ₂ , -RSO ₂ M, -PO ₃ HM, -PO ₃ M ₂ , -SO ₂ It is preferably at least one hydrophilic group selected from the group consisting of NHCOR, -NH ₃ , and -NR _3.

In these chemical formulas, M represents a hydrogen atom, an alkali metal, ammonium, a phenyl group which may have a substituent, or an organic ammonium, and R is an alkyl group or a substituent having 1 to 12 carbon atoms. Represents a naphthyl group which may have a group. Further, the above M and R are selected independently of each other.

The self-dispersing pigment is specifically produced by subjecting the pigment to physical treatment and / or chemical treatment to bond (graft) the hydrophilic group to the surface of the pigment. Specific examples of the physical treatment include vacuum plasma treatment. Further, as the chemical treatment, specifically, a wet oxidation method of oxidizing with an oxidizing agent in water, a method of binding a carboxyl group via a phenyl group by binding p-aminobenzoic acid to the pigment surface, and the like are used. Can be mentioned. Among these, the pigment is more preferably ozone-oxidized or phosphorylated carbon black, and particularly preferably ozone-oxidized carbon black.

The self-dispersing pigment preferably satisfies the condition represented by the following relational expression (3). As a result, the fastness of printed matter and the stability of continuous printing tend to be superior due to the suppression of the generation of foreign substances caused by the self-dispersing pigment.
1.0 ≤ (φ6 / φ5) ≤ 10 ... (3)
(In the formula, φ5 indicates the volume average particle size of D50 of the self-dispersing pigment in a solution containing 20% by mass of the self-dispersing pigment and 80% by mass of water, and φ6 is 90% by mass of the self-dispersing type. The volume average particle size of D50 of the autocovariant pigment in a solution containing the pigment and 10% by mass of water is shown.)

Further, (φ6 / φ5) is more preferably 1.0 or more and 8.0 or less, further preferably 1.0 or more and 6.5 or less, and particularly preferably 3.0 or more and 6.5 or less. ..

The volume average particle size of D50 of the self-dispersing pigment in the present specification can be measured by the method described in Examples described later.

In the ink composition, the content of the pigment particles is preferably 1.0% by mass or more and 20% by mass or less, and more preferably 3.0% by mass or more, based on the total amount (100% by mass) of the ink composition. It is 15% by mass or less, more preferably 5.0% by mass or more and 10% by mass or less. When the content of the pigment particles is within the above range, the printed matter fastness and continuous printing stability tend to be superior.

<Water>
The ink composition of this embodiment contains water. Examples of water include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water, and ultrapure water from which ionic impurities have been removed as much as possible. Further, when water sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide or the like is used, it is possible to prevent the growth of mold and bacteria when the aggregated liquid is stored for a long period of time. This tends to further improve storage stability.

<Organic solvent>
The ink composition of this embodiment contains glycol ether. The glycol ether is not particularly limited as long as it can be used together with water. Further, an organic solvent other than glycol ether may be further contained. Examples of organic solvents other than glycol ether include cyclic nitrogen compounds, aprotic polar solvents, monoalcohols, and alkyl polyols (eg, glycerin).

The glycol ether is not particularly limited, and examples thereof include glycol diethers and glycol monoethers.

Specific examples of glycol diether are not particularly limited, but ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and tri. Ethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether Can be mentioned.

Specific examples of glycol monoether are not particularly limited, but ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and the like. Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether , Propropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

The content of glycol ether is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less, based on the total amount (100% by mass) of the ink composition. More preferably, it is 1.0% by mass or more and 5.0% by mass or less. When the content of glycol ether is within the above range, the fastness of printed matter and the stability of continuous printing tend to be superior.

<Surfactant>
The ink composition preferably further contains a surfactant from the viewpoint of continuous printing stability. The surfactant is not particularly limited, and examples thereof include an acetylene glycol-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant.

The acetylene glycol-based surfactant is not particularly limited, but is 2,4,7,9-tetramethyl-5-decine-4,7-diol and 2,4,7,9-tetramethyl-5-decine-. One selected from alkylene oxide adducts of 4,7-diol and alkylene oxide adducts of 2,4-dimethyl-5-decine-4-ol and 2,4-dimethyl-5-decine-4-ol. The above is preferable. Commercially available products of acetylene glycol-based surfactants are not particularly limited, but for example, E series such as Orfin 104 series and Orfin E1010 (trade name manufactured by Air Products Japan, Inc.), Surfinol 104PG50, 465, 61, DF110D (trade name manufactured by Nissin Chemical Industry CO., Ltd.) can be mentioned. The acetylene glycol-based surfactant may be used alone or in combination of two or more.

The fluorosurfactant is not particularly limited, and is, for example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylic acid salt, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, and the like. Perfluoroalkylamine oxide compounds can be mentioned. Commercially available products of fluorine-based surfactants are not particularly limited, but for example, S-144, S-145 (trade name, manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Florard-FC4430 (the above products). Name: FSO, FSO-100, FSN, FSN-100, FS-300 (trade name, manufactured by DuPont); FT-250, 251 (trade name, manufactured by Neos Co., Ltd.) Can be mentioned. The fluorine-based surfactant may be used alone or in combination of two or more.

The silicone-based surfactant is not particularly limited, and examples thereof include polysiloxane-based compounds and polyether-modified organosiloxanes. The commercially available silicone-based surfactant is not particularly limited, but specifically, SAG503A (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (trade name, manufactured by Big Chemie), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF -615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (trade names, Shin-Etsu) (Manufactured by Chemical Co., Ltd.) The silicone-based surfactant may be used alone or in combination of two or more.

The content of the surfactant is preferably 0.05% by mass or more and 2.5% by mass or less, and more preferably 0.05% by mass or more and 1.5% by mass, based on the total amount (100% by mass) of the ink composition. It is mass% or less. When the content of the surfactant is within the above range, the printed matter fastness and continuous printing stability tend to be superior.

Other components of the ink composition include softeners, waxes, dissolution aids, viscosity regulators, pH adjusters such as triisopropanolamine, moisturizers, antioxidants, fungicides / preservatives, fungicides, and corrosion. Various additives such as an inhibitor and a chelating agent for capturing metal ions affecting the dispersion (for example, sodium ethylenediaminetetraacetate) can also be appropriately contained.

[Container]
The container of the present embodiment includes a container made of a flexible film and the above-mentioned ink composition contained in the container. Further, the water absorption rate of the film is 3% or less. When the water absorption rate of the film is in such a range, even when the films stick to each other, the water absorption from the ink composition existing at the sticking portion is suppressed, and foreign matter tends to be less likely to be generated. It is in.

In the container, the film has two or more layers, and it is preferable that the two or more layers include a layer containing at least nylon because the water absorption rate of the film tends to be easily controlled within the above range. The layer structure and material of the film are not particularly limited, and examples thereof include an ink container described later.

Hereinafter, the housing that can be used in the present embodiment will be exemplified by using the printing system and the housing shown in FIGS. 1 to 6, but the housing of the present embodiment is the printing system and the housing shown in FIGS. 1 to 6. It is not limited to the mode of the body, and may have an appropriate configuration.

As shown in FIG. 1, the printing system in the present embodiment includes a printer 3 which is an example of a printing device, and an ink supply device 4. The printer 3 has a transport device 5, a recording unit 6, a moving device 7, a relay device 9, and a control unit 11. Note that FIG. 1 has an XYZ axis, which is a coordinate axis orthogonal to each other. The figures shown below are also provided with XYZ axes as necessary. In the present embodiment, the state in which the printing system 1 is arranged on the horizontal plane (XY plane) defined by the X-axis and the Y-axis is the usage state of the printing system 1. The Z axis is an axis orthogonal to a horizontal plane. In the used state of the printing system 1, the Z-axis direction is vertically upward. Then, in the state of use of the printing system 1, in FIG. 1, the −Z axis direction is the vertical downward direction. In each of the XYZ axes, the direction of the arrow indicates the + (positive) direction, and the direction opposite to the direction of the arrow indicates the − (negative) direction.

The transport device 5 intermittently transports the recording medium P such as recording paper in the Y-axis direction. The recording unit 6 prints the ink composition on the recording medium P transported by the transport device 5. The moving device 7 reciprocates the recording unit 6 along the X axis. The ink supply device 4 supplies the ink composition to the recording unit 6 via the relay device 9. The relay device 9 is provided between the ink supply device 4 and the recording unit 6, and relays the ink composition from the ink supply device 4 to the recording unit 6. The control unit 11 controls the drive of each of the above configurations.

As shown in FIG. 1, the transfer device 5 includes a drive roller 12A, a driven roller 12B, and a transfer motor 13. The drive roller 12A and the driven roller 12B are configured to be rotatable so that their outer circumferences are in contact with each other. The transfer motor 13 generates power for rotationally driving the drive roller 12A. The power from the transfer motor 13 is transmitted to the drive roller 12A via the transmission mechanism. Then, the recorded medium P sandwiched between the driving roller 12A and the driven roller 12B is intermittently conveyed in the Y-axis direction.

The recording unit 6 includes a carriage 17 and a recording head 19. The recording head 19 ejects the ink composition as ink droplets and records on the recording medium P. The carriage 17 is equipped with a recording head 19. The recording head 19 is connected to the control unit 11 via a flexible cable 31. The ejection of ink droplets from the recording head 19 is controlled by the control unit 11.

As shown in FIG. 1, the moving device 7 includes a timing belt 43, a carriage motor 45, and a guide shaft 47. The timing belt 43 is stretched between the pair of pulleys 41A and 41B. The pair of pulleys 41A and 41B are arranged along the X axis. Therefore, the timing belt 43 is stretched along the X axis. The carriage motor 45 generates power for rotationally driving the pulley 41A. The guide shaft 47 extends along the X axis. Both ends of the guide shaft 47 are supported by a housing (not shown), and guide the carriage 17 along the X axis.

The carriage 17 is fixed to a part of the timing belt 43. Power is transmitted to the carriage 17 from the carriage motor 45 via the pulley 41A and the timing belt 43. The carriage 17 is configured to be reciprocally movable along the X-axis by the transmitted power.

As shown in FIG. 1, the ink supply device 4 has an ink container 51, which is an example of the container, and a case 53. In this embodiment, the ink supply device 4 includes a plurality of (four in this embodiment) ink containers 51. The four ink containers 51 are housed in the case 53. The four ink containers 51 contain different types of ink compositions. In this embodiment, the yellow (Y), magenta (M), cyan (C), and black (K) ink compositions are contained in different ink containers 51. The case 53 is provided with a detachable unit (not shown) that supports the ink container 51. The four ink containers 51 are detachably supported by the detachable unit. Each ink container 51 has an ink bag as a storage unit. The ink composition is sealed in an ink bag made of a flexible film. In the printing system 1, when the ink composition in the ink bag is consumed, it is replaced with a new ink container 51.

An ink supply tube 57 is connected to the ink bag of each ink container 51 via a detachable unit (not shown). The ink supply tube 57, which is an example of the flow path member, is connected from the ink supply device 4 to the relay device 9. The relay device 9 has a pump unit 59. The pump unit 59 pumps up the ink composition in the ink container 51 mounted on the ink supply device 4. Then, the pump unit 59 sends the ink composition pumped from the ink container 51 to the recording head 19 via the ink supply tube 61. As a result, the ink in the ink container 51 is supplied from the ink supply device 4 to the recording head 19 via the relay device 9. Then, the ink composition supplied to the recording head 19 is ejected as ink droplets from a nozzle (not shown) directed toward the recording medium P side.

In the liquid injection system 1 having the above configuration, the drive of the transfer motor 13 is controlled by the control unit 11, and the transfer device 5 intermittently conveys the recording medium P in the Y-axis direction while facing the recording head 19. .. At this time, the control unit 11 controls the drive of the carriage motor 45 to reciprocate the carriage 17 along the X-axis, and controls the drive of the recording head 19 to eject ink droplets at a predetermined position. .. By such an operation, dots are formed on the recording medium P, and printing is performed on the recording medium P based on recording information such as image data.

As shown in FIG. 2, for example, the ink container 51 has an ink bag 71, which is an example of the storage unit, and a flow path unit 83. Here, in the present embodiment, a plurality of types (4 types) of ink containers 51 will be illustrated. In the following, when each of the four types of ink containing bodies 51 is identified, the four types of ink containing bodies 51 are referred to as an ink containing body 51A, an ink containing body 51B, an ink containing body 51C, and an ink containing body 51D, respectively. Notated. In the four types of ink containers 51, the configurations and dimensions of the ink bags 71 are different from each other.

As shown in FIG. 2, the ink container 51A has an ink bag 71A and a flow path unit 83. As shown in FIG. 3, the ink container 51B has an ink bag 71B and a flow path unit 83. As shown in FIG. 4, the ink container 51C has an ink bag 71C and a flow path unit 83. As shown in FIG. 5, the ink container 51D has an ink bag 71D and a flow path unit 83. The four types of ink containers 51 have the same configuration as each other except for the ink bag 71. Therefore, in the following, the details of the configuration will be described with the ink container 51A as an example, and the description of the ink container 51B to the ink container 51D will be omitted.

As shown in FIG. 6, the ink bag 71 has at least two flexible film materials 72 (film material 72A and film material 72B). The ink bag 71A has a structure in which three film materials 72 are joined to each other. In the following, when the three film materials 72 are mutually identified, the three film materials 72 are referred to as a film material 72A, a film material 72B, and a film material 72C, respectively. The film material 72A and the film material 72B are joined so as to face each other. In the ink container 51, the direction in which the two film materials 72 (film material 72A and film material 72B) face each other is referred to as the first direction K1. Further, the direction in which the handle portion 131 of the flow path unit 83 protrudes from the ink bag 71 is referred to as the second direction K2. In the printing system 1, the second direction K2 corresponds to the Z-axis direction. Further, the direction that intersects (orthogonally) both the first direction K1 and the second direction K2 is referred to as the third direction K3.

The film material 72A and the film material 72B are welded to each other in the peripheral region 85 in a state of being overlapped with each other. The film material 72C is sandwiched between the film material 72A and the film material 72B in the first direction K1. The peripheral edge of the film material 72C is welded to the film material 72A and the film material 72B in a state of being overlapped with the peripheral region 85. As a result, the ink bag 71 has a bag-like shape with the film material 72C as the bottom. The ink composition is housed inside the ink bag 71. Therefore, the ink bag 71 has a function as an ink accommodating portion for accommodating an ink composition which is an example of a liquid. In FIG. 6, the peripheral region 85 is hatched in order to show the configuration in an easy-to-understand manner. Further, FIG. 6 shows a state in which the film material 72C is cut between the film material 72A and the film material 72B.

When such an ink bag 71 is used, even if the ink composition is consumed, new gas or the like is not supplied to the ink bag 71, so that the ink composition contained in the ink bag 71 is simply reduced. Only. As a result, the reduced ink composition is unevenly distributed on the lower side in the ink bag 71, while the film materials 72A and 72B on the upper part of the ink bag 71 are in a state of being stuck to each other. In the present embodiment, even when the film materials 72A and 72B in the ink bag 171 are stuck to each other, the generation of foreign substances is suppressed, and a printed matter having excellent printed matter fastness can be obtained.

In particular, when the size of the ink bag 71 is large, the area of the portion where the film materials 72A and 72B on the upper part of the ink bag 71 stick to each other becomes large, and the amount of foreign matter generated tends to increase. Further, when the size of the ink bag 71 is large, the time until the ink composition in the ink bag 71 is consumed becomes relatively long, so that the film materials 72A and 72B on the upper part of the ink bag 71 are attached to each other. The time tends to be longer and the amount of foreign matter generated tends to increase.

The flow path unit 83 is sandwiched between the film material 72A and the film material 72B in a part of the peripheral region 85. In a part of the peripheral region 85, the flow path unit 83 and the film material 72A are welded to each other. Similarly, in a part of the peripheral region 85, the flow path unit 83 and the film material 72B are welded to each other. Therefore, a part of the peripheral region 85 in which the flow path unit 83 is sandwiched between the film material 72A and the film material 72B is a joint portion between the ink bag 71 and the flow path unit 83. The flow path unit 83 is provided with a welding portion 86. Each of the film material 72A and the film material 72B is welded to the welded portion 86 in a state where the welded portion 86 is sandwiched between the film material 72A and the film material 72B. The film material 72A, the film material 72B, and the flow path unit 83 are joined to each other to form an ink bag 71 having the film material 72C at the bottom.

As the materials of the film material 72A, the film material 72B, and the film material 72C, for example, polyethylene terephthalate (PET), nylon, polyethylene, polypropylene, polyimide, cellophane, polyester, acetate, and polyamide-imide can be adopted, respectively. Further, a laminated structure in which films composed of these materials are laminated can also be adopted. In such a laminated structure, for example, the outer layer can be made of PET or nylon having excellent impact resistance and low water absorption, and the inner layer can be made of polyethylene having excellent ink resistance. Further, a film or the like having a layer on which aluminum or the like is vapor-deposited can also be adopted. This makes it possible to control the water absorption rate of the film and enhance the gas barrier property of the film. The ink bag 71B of the ink container 51B (FIG. 3) is composed of three film materials 72 like the ink bag 71A. The ink bag 71A and the ink bag 71B are each in a form called a pouch type. In the two types of the ink container 51C and the ink container 51D (FIGS. 4 and 5), each ink bag 71 is composed of two film materials 72 (film material 72A and film material 72B). The four types of ink bag 71C and ink bag 71D are each in a form called a pillow type.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to the following examples.

[Production Example 1] Resin particles 1
900 g of ion-exchanged water and 3 g of sodium lauryl sulfate were charged in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature was raised to 70 ° C. while substituting nitrogen under stirring. Keep the internal temperature at 70 ° C., add 4 g of potassium persulfate as a polymerization initiator, and after dissolution, stir 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 300 g of styrene, 640 g of butyl acrylate and 30 g of methacrylic acid in advance. The emulsion prepared in addition to the bottom was continuously added dropwise into the reaction solution over 4 hours. After completion of the dropping, aging was carried out for 3 hours. After cooling the obtained aqueous emulsion to room temperature, ion-exchanged water and a 5% aqueous sodium hydroxide solution were added to adjust the solid content to 40% by mass and pH 8. The zeta potential of the obtained aqueous emulsion resin particle 1 was -23 mV.

[Production Example 2] Resin particles 2
900 g of ion-exchanged water and 1 g of sodium lauryl sulfate were charged in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature was raised to 70 ° C. while substituting nitrogen under stirring. Keep the internal temperature at 70 ° C., add 4 g of potassium persulfate as a polymerization initiator, and after dissolution, stir 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 365 g of styrene, 545 g of butyl acrylate and 30 g of methacrylic acid in advance. The emulsion prepared in addition to the bottom was continuously added dropwise into the reaction solution over 4 hours. After completion of the dropping, aging was carried out for 3 hours. After cooling the obtained aqueous emulsion to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 40% by mass and pH 8. The zeta potential of the obtained aqueous emulsion resin particles 2 was −53 mV.

[Production Example 3] Resin particles 4
900 g of ion-exchanged water and 1 g of sodium lauryl sulfate were charged in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature was raised to 70 ° C. while substituting nitrogen under stirring. The internal temperature is kept at 70 ° C., 4 g of potassium persulfate is added as a polymerization initiator, and after dissolution, 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 615 g of styrene, 295 g of butyl acrylate and 30 g of methacrylic acid are stirred in advance. The emulsion prepared in addition to the above was continuously added dropwise into the reaction solution over 4 hours. After completion of the dropping, aging was carried out for 3 hours. After cooling the obtained aqueous emulsion to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 40% by mass and pH 8. The zeta potential of the obtained aqueous emulsion, resin particles 4, was −5 mV.

[Production Example 4] Resin particles 5
900 g of ion-exchanged water and 3 g of sodium lauryl sulfate were charged in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature was raised to 70 ° C. while substituting nitrogen under stirring. The internal temperature is kept at 70 ° C., 4 g of potassium persulfate is added as a polymerization initiator, and after dissolution, 450 g of ion-exchanged water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 675 g of styrene, 235 g of butyl acrylate, and 30 g of methacrylic acid are stirred in advance. The emulsion prepared in addition to the above was continuously added dropwise into the reaction solution over 4 hours. After completion of the dropping, aging was carried out for 3 hours. After cooling the obtained aqueous emulsion to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content to 40% by mass and pH 8. The zeta potential of the resin particles 5 of the obtained aqueous emulsion was −10 mV.

[Resin particles]
The trade name "Takelac W6110" manufactured by Mitsui Chemicals Co., Ltd. was prepared as the resin particles 3, and any of the resin particles 1 to 5 was adjusted with ultrapure water so that the solid content was 20% by mass, and the resin particles were 20% by mass. Aqueous solution 1 of the above was prepared. The composition of the aqueous solution 1 is shown below. Further, the following aqueous solutions 2 to 5 were prepared in the same manner as in the aqueous solution 1.
Aqueous solution 1: 20% by mass of resin particles 1 to 5 and 80% by mass of ultrapure water aqueous solution 2: 90% by mass of resin particles 1 to 5 and 10% by mass of ultrapure water aqueous solution 3 : Any of 20% by mass of resin particles 1 to 5, 5% by mass of triethylene glycol monobutyl ether, and 75% by mass of ultra-pure water aqueous solution 4: 90% by mass of any of resin particles 1 to 5, 5% by mass % Triethylene glycol monobutyl ether, 5% by mass ultra-pure water aqueous solution 5: 20% by mass self-dispersing pigment, 80% by mass ultra-pure water aqueous solution 6: 90% by mass self-dispersing pigment, and 10. Mass% ultra-pure water

For each of the aqueous solution 1, the aqueous solution 2, the aqueous solution 3, and the aqueous solution 4, the volume average particle diameter of D50 was measured with "Microtrac Nanotrac Wave EX150" (trade name manufactured by Microtrac Bell), and each resin particle 1 to 5 was measured. The volume average particle diameter of D50 was set to φ1, φ2, φ3, and φ4. Similarly, the volume average particle diameter of D50 was measured for the aqueous solution 5 and the aqueous solution 6, and the volume average particle diameters of the self-dispersing pigment D50 were set to φ5 and φ6. Further, (φ2 / φ1) and (φ4 / φ3) were obtained for each of the resin particles 1 to 5, and (φ6 / φ5) was obtained for the self-dispersing pigment. The results are shown in Tables 2 and 3 below.

[Materials and Containers for Ink Compositions]
The main materials and inclusions for the ink composition used in the preparation of the following recordings are as follows.
[Ink composition]
[Pigment]
Self-dispersing carbon black Aqua-Black162 (registered trademark, manufactured by Tokai Carbon Co., Ltd.)
[Resin particles]
Resin particles 1 (resin: styrene acrylic resin)
Resin particles 2 (resin: styrene acrylic resin)
Resin particles 3 (trade name "Takelac W6110" manufactured by Mitsui Chemicals, resin: urethane resin)
Resin particles 4 (resin: styrene acrylic resin)
Resin particles 5 (resin: styrene acrylic resin)
〔Organic solvent〕
Glycerin Triethylene Glycol Monobutyl Ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Surfactant]
Orfin E1010 (trade name manufactured by Air Products & Chemicals)
Surfinol 104PG50 (trade name manufactured by Nisshin Kagaku Kogyo Co., Ltd.)
[PH regulator]
Triisopropanolamine [water]
Pure water [container]
〔the film〕
Nylon Polyethylene Polypropylene Polyethylene terephthalate Polyimide Cellophane [Shape]
What is shown in FIGS. 3 to 5

[Water absorption rate]
The water absorption rate [% · 24 hours] of each film was measured according to the method specified in JIS7209 (Plastic water absorption rate and boiling water water absorption rate test method). Specifically, each film was submerged and the mass increase per unit time was measured and determined. The results are shown in Table 1 below.

[Preparation of ink composition]
Each material was mixed with the compositions shown in Tables 2 and 3 below and stirred well to obtain an ink composition. In Tables 2 and 3 below, the unit of the numerical value is mass%, the numerical value is the solid content concentration, and the total is 100.0 mass%.

[Continuous printing stability]
Each ink composition prepared above was injected into each container shown in Table 2 or Table 3. The injection amount was about 1/10 of the capacity of each container. Then, the container containing the ink composition was left to stand in an environment of 60 ° C. for one week. After that, each housing was attached to an inkjet printer (product name "PX-7050FX" manufactured by Seiko Epson Co., Ltd.), initial filling was performed, and a nozzle check was performed to confirm that no nozzles were missing. Then, the nozzles after printing 100 sheets continuously using plain paper (XeroxP paper) using the ISO / IEC 24734 image pattern were checked, and the continuous printing stability was evaluated according to the following evaluation criteria. The results are shown in Tables 2 and 3.
(Evaluation criteria)
A: The number of missing nozzles is less than 3 B: The number of missing nozzles is 3 or more and less than 5 C: The number of missing nozzles is 5 or more

[Printed matter robustness]
Each ink composition prepared above is filled in each container shown in Table 2 or Table 3, and the container is mounted on an inkjet printer (product name "PX-7050FX" manufactured by Seiko Epson), and plain paper (plain paper (product name "PX-7050FX")). An ISO / IEC 24734 image pattern was printed using XeroxP paper). After the printed matter was left at room temperature and humidity for one week, the printed part of the printed matter was line-marked with a highlighter pen 300 gf manufactured by Zebra, and the robustness of the printed matter was evaluated according to the following evaluation criteria. The results are shown in Tables 2 and 3.
(Evaluation criteria)
A: No bleeding can be confirmed even if the printed part is line-marked twice.
B: No bleeding can be confirmed even if the printed portion is line-marked once, and bleeding can be slightly confirmed by line-marking twice.
C: No bleeding can be confirmed even if the printed portion is line-marked once, and bleeding can be confirmed by line-marking twice.
D: The printed part is line-marked once and bleeding can be confirmed.

1 ... printing system, 3 ... printer, 4 ... ink supply device, 5 ... transfer device, 6 ... recording unit, 7 ... moving device, 9 ... relay device, 11 ... control unit, 12A ... drive roller, 12B ... driven roller, 13 ... Conveyor motor, 17 ... Carriage, 19 ... Recording head, 31 ... Flexible cable, 41A, 41B ... Pulley, 43 ... Timing belt, 45 ... Carriage motor, 47 ... Guide shaft, 51, 51A, 51B, 51C, 51D, 51E, 51F ... Ink container, 53 ... Case, 57 ... Ink supply tube, 59 ... Pump unit, 61 ... Ink supply tube, 71, 71A, 71B, 71C, 71D ... Ink bag, 72, 72A, 72B, 72C ... Film material, 83 ... Flow path unit, 85 ... Peripheral region, 86 ... Welding part, 93 ... Tube, 131 ... Handle part, K1 ... 1st direction, K2 ... 2nd direction, K3 ... 3rd direction, P ... Recorded Medium.

Claims (9)

It comprises an accommodating portion made of a flexible film, and an ink composition contained in the accommodating portion and containing resin particles, a pigment, glycol ether, and water.
The resin particles, meets the condition represented by the following equation (1),
The zeta potential of the resin particles in the solution containing 20% by mass of the resin particles and 80% by mass of water is -60 mV or more and -15 mV or less.
Containment body.
1.0 ≤ (φ2 / φ1) ≤ 12.5 ... (1)
(In the formula, φ1 indicates the volume average particle diameter of D50 of the resin particles in a solution containing 20% by mass of the resin particles and 80% by mass of water, and φ2 is 90% by mass of the resin particles and 10 The volume average particle diameter of D50 of the resin particles in the solution containing mass% of water is shown.) The resin particles satisfy the condition represented by the following relational expression (2).
The containment according to claim 1.
1.0 ≤ (φ4 / φ3) ≤ 20 ... (2)
(In the formula, φ3 indicates the volume average particle diameter of D50 of the resin particles in a solution containing 20% by mass of the resin particles, 5% by mass of triethylene glycol monobutyl ether and 75% by mass of water, and φ4 is The volume average particle diameter of D50 of the resin particles in a solution containing 90% by mass of the resin particles, 5% by mass of triethylene glycol monobutyl ether and 5% by mass of water is shown.) The pigment is an autocovariant pigment that satisfies the condition represented by the following relational expression (3).
The containment according to claim 1 or 2.
1.0 ≤ (φ6 / φ5) ≤ 10 ... (3)
(In the formula, φ5 represents the volume average particle diameter of D50 of the self-dispersing pigment in a solution containing 20% by mass of the self-dispersing pigment and 80% by mass of water, and φ6 is 90% by mass of the said self-dispersing pigment. The volume average particle diameter of D50 of the self-dispersing pigment in a solution containing the self-dispersing pigment and 10% by mass of water is shown.) The glass transition temperature of the resin particles is −50 ° C. or higher and 0 ° C. or lower.
The housing according to any one of claims 1 to 3. The resin particles contain one or more selected from the group consisting of (meth) acrylic resin, urethane resin, epoxy resin, polyolefin resin, and styrene acrylic resin.
The container according to any one of claims 1 to 4. The content of the resin particles is 0.5% by mass or more and 5.0% by mass or less with respect to the total amount of the ink composition.
The container according to any one of claims 1 to 5. The pigment is an ozone-oxidized carbon black pigment.
The housing according to any one of claims 1 to 6. The film has two or more layers
The two or more layers include at least a layer containing nylon.
The container according to any one of claims 1 to 7. The water absorption rate of the film is 3% or less.
The housing according to any one of claims 1 to 8.

Images